CN104238289A - Process for producing electrophotographic photosensitive member - Google Patents

Process for producing electrophotographic photosensitive member Download PDF

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Publication number
CN104238289A
CN104238289A CN201410277245.9A CN201410277245A CN104238289A CN 104238289 A CN104238289 A CN 104238289A CN 201410277245 A CN201410277245 A CN 201410277245A CN 104238289 A CN104238289 A CN 104238289A
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quality
emulsion
electrophotographic photosensitive
photosensitive element
ether
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CN104238289B (en
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奥田笃
大垣晴信
关户邦彦
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Canon Inc
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Canon Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0525—Coating methods
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/142—Inert intermediate layers

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Provided is a process for producing an electrophotographic photosensitive member having high uniformity of the surface of its undercoat layer by which the usage of an organic solvent is reduced and the stability of an application liquid for an undercoat layer after its long-term storage is improved in the step of forming the undercoat layer. The process for producing an electrophotographic photosensitive member includes the steps of: preparing a solution containing a liquid whose solubility in water at 25 DEG C and 1 atmosphere is 3.0 mass% or less and an electron transporting substance; preparing an emulsion by dispersing the solution in water; forming a coat of the emulsion on a support; and forming the undercoat layer by heating the coat.

Description

The production method of electrophotographic photosensitive element
Technical field
The present invention relates to the production method of electrophotographic photosensitive element.
Background technology
The electrophotographic photosensitive element comprising organic photoconductive material (hereinafter referred to " charge generation substance ") is known as the electrophotographic photosensitive element that will be arranged on electronic photographing device.At present, above-mentioned electrophotographic photosensitive element is the electrophotographic photosensitive element for the handle box of electronic photographing device or the main flow of electronic photographing device, and scale of inputization is produced.In this electrophotographic photosensitive element, often use and be separated to its each layer by each function needed for electrophotographic photosensitive element and improve the laminated electrophotographic Electrifier frame, photoreceptor of characteristic.Adopt by undercoat, charge generation layer and hole transporting layer being laminated to successively structure that supporting mass the obtains major constituents as laminated electrophotographic Electrifier frame, photoreceptor.
Usual employing relates to functional material and is dissolved in organic solvent to prepare coating solution (coating fluid) and described solution to be coated on the production method of the method on supporting mass as laminated electrophotographic Electrifier frame, photoreceptor.Be desirably in recent years in the step forming each layer film and reduce organic solvent.The proposal that proposal as described below is used as the organic solvent of the undercoat of reduction layer die mould electrophotographic photosensitive element is carried out in the layer of scattered electrons transportation of substances.
Japanese Patent Application Laid-Open No.2012-128397 proposes to relate to following method: produce the aqueous dispersions comprising the particle of polyolefin resin particles and each self-contained electron transport material; Supporting mass is formed the film of described dispersion liquid; Undercoat is formed to make polyolefin resin particles melting with by the described film of heating.In Japanese Patent Application Laid-Open No.2012-128397, form the undercoat wherein having disperseed the particle of each self-contained electron transport material.
But, as the result of the research that the present inventor carries out, method disclosed in Japanese Patent Application Laid-Open No.2012-128397 is form wherein electron transport material with the method for the undercoat of the state of the particle of each self-contained electron transport material dispersion, and thus the homogeneity of the stability of aqueous dispersions during its long storage periods and base coating surface is easy to reduce in some cases.Therefore, the production method reducing organic solvent and the improvement stability of coating liquid for undercoat layer and the homogeneity of base coating surface when forming undercoat is desirably in.
Summary of the invention
The object of the present invention is to provide the production method of electrophotographic photosensitive element, particularly in the step forming undercoat, the consumption of organic solvent reduces and the stability improvement of coating liquid for undercoat layer after its long storage periods, the production method of the electrophotographic photosensitive element that the homogeneity of base coating surface is high.
The present invention relates to the production method of electrophotographic photosensitive element, described electrophotographic photosensitive element comprises supporting mass, the undercoat be formed on supporting mass, the hole transporting layer that is formed at the charge generation layer on undercoat and is formed on charge generation layer, and described method comprises the steps: to prepare and comprises following solution: in the water under 25 DEG C and 1 atmospheric pressure, solubleness is liquid and the electron transport material of below 3.0 quality %; By described Solution Dispersion is prepared emulsion in water; Supporting mass is formed the film of described emulsion; Undercoat is formed with by heating film.
According to one embodiment of the invention, the consumption of organic solvent can be provided to reduce and coating liquid for undercoat layer (emulsion) stability improvement after its long storage periods, electrophotographic photosensitive element that the homogeneity of base coating surface is high.
With reference to accompanying drawing, further feature of the present invention becomes apparent in the description from following exemplary.
Accompanying drawing explanation
Fig. 1 illustrates the figure comprising the example of the schematic configuration of the electronic photographing device of the handle box comprising electrophotographic photosensitive element.
Fig. 2 is the figure of the example of the layer structure that electrophotographic photosensitive element is described.
Embodiment
Now, preferred embodiment of the present invention is described with reference to the accompanying drawings in detail.
The production method of electrophotographic photosensitive element of the present invention comprises the steps: as first step, and it is the step of the liquid of below 3.0 quality % and the solution of electron transport material and the step by described Solution Dispersion being prepared in water emulsion that preparation is included in solubleness in the water under 25 DEG C and 1 atmospheric pressure.Described method comprises the steps: the film forming emulsion on supporting mass further; Undercoat is formed with by the described film of heating.
From the viewpoint of stability improving coating liquid for undercoat layer (emulsion), in the water under 25 DEG C and 1 atmospheric pressure, solubleness is that the liquid of more than 5.0 quality % is preferably mixed in described solution further.
The present inventor infer of the present invention comprise the consumption reducing organic solvent in the production method of the electrophotographic photosensitive element of the step forming undercoat and the reason of stability improving coating liquid for undercoat layer as described below.
In the present invention, the coating liquid for undercoat layer wherein having reduced the consumption of organic solvent can be provided by means of the emulsion obtained in water by Solution Dispersion by preparation, and described solution is by being obtain in the liquid (hydrophobic solvent) of below 3.0 quality % by least electron transport substance dissolves solubleness in the water under 25 DEG C and 1 atmospheric pressure.Emulsion of the present invention is in the state that wherein oil droplet (also referred to as " emulsion particle ") is dispersed in water because of Solution Dispersion in the water wanting emulsification.In production method of the present invention, water-insoluble electron transport material and undercoat form component and can be used as it is, and are dissolved in hydrophobic organic solvent before emulsification because electron transport material and undercoat form component.Usually, electron transport material water fast, even if or when this material is soluble in water, its concentration is low.In addition, its electrology characteristic is not enough in many cases.Therefore, this material is difficult to use in water-based coating fluid, and the homogeneity of the stability of coating liquid for undercoat layer and base coating surface may be not enough.On the other hand, in production method of the present invention, the stability of coating liquid for undercoat layer and the homogeneity of base coating surface can be improved due to preparation emulsion.
In addition, in the present invention, be that both the liquid (hydrophilic solvent) of more than 5.0 quality % is preferably used as organic solvent by solubleness in hydrophobic solvent and the water under 25 DEG C and 1 atmospheric pressure owing to improving emulsion intercalation method extraordinarily.When by the Solution Dispersion obtained by means of using hydrophobic solvent and hydrophilic solvent to dissolve at least electron transport material is prepared emulsion in water, obtain following result: even if when emulsion long storage periods, emulsion intercalation method is also high, and in production, this is favourable.When emulsion comprises both hydrophobic solvent and hydrophilic solvent, in emulsion, the hydrophilic solvent in oil droplet is towards aqueous phase fast transferring, and it is little that oil droplet becomes especially, and the concentration of electron transport material in oil droplet increases.Can imagine due to aforesaid reason, oil droplet is in the fine grain state close to solid matter, and with wherein by compared with the situation that is used alone the emulsion that hydrophobic solvent is produced, the appearance of the gathering of oil droplet can be suppressed extraordinarily.Can also imagine that hydrophilic solvent has amphiphilic character (amphipathic property) thus is dissolved in water and oil, thus hydrophilic solvent image surface activating agent is the same works thus suppresses the gathering of oil droplet (coalescent) in oil droplet.General due to previous reasons, even if the disperse state in emulsion also can be maintained and be improved emulsion intercalation method after its long storage periods.
Hereinafter, describe the production method of electrophotographic photosensitive element of the present invention and form the material of electrophotographic photosensitive element.Electrophotographic photosensitive element of the present invention comprises supporting mass, the undercoat be formed on supporting mass, the hole transporting layer that is formed at the charge generation layer on undercoat and is formed on charge generation layer.
Fig. 2 is the figure of the example of the layer structure that electrophotographic photosensitive element is described.In Fig. 2, supporting mass is represented by Reference numeral 21, and undercoat is represented by Reference numeral 22, and charge generation layer is represented by Reference numeral 23, and hole transporting layer is represented by Reference numeral 24.
Although be widely used as common electrophotographic photosensitive element by photographic layer (charge generation layer or hole transporting layer) is formed at the cylindric electrophotographic photosensitive element that cylindric supporting mass obtains, the shape of band shape or sheet also can be used.
(undercoat)
Electron transport material for undercoat is preferably organic electronic transportation of substances.The example of electron transport material comprises imide compound, naphtoquinone compounds, benzimidazole compound and cyclopentadienyl compounds.
Imide compound preferably has the compound of cyclic imide structure, and the compound preferably represented by following formula (1).
In formula (1), R 1and R 2represent substituted or unsubstituted alkyl, substituted or unsubstituted phenyl or substituted or unsubstituted pyridine radicals independently of one another.The substituent example of the substituting group of alkyl replaced, the substituting group of the phenyl of replacement and the pyridine radicals of replacement comprises alkyl, haloalkyl, hydroxyalkyl, halogen atom, hydroxyl, carboxyl, mercapto, amino, alkoxy, cyano group, nitro, phenyl and phenyl nitrence base (phenylazenyl group).N represents the repeat number of bracket inner structure, and represents 1 or 2.
Naphtoquinone compounds is such as, has the compound of paraquinoid structure (para-quinoid structure) or adjacent quinoid structure (ortho-quinoid structure).In addition, the compound with the structure that wherein aromatic ring condenses mutually allows, and the compound with the wherein interconnective structure of multiple quinoid structure allows.The compound that naphtoquinone compounds is preferably represented by following formula (2) or following formula (3).
In formula (2), R 11to R 18represent hydrogen atom, alkyl independently of one another or pass through by R 11to R 18the divalent group represented by-CH=CH-CH=CH-of the bonding formation of the adjacent group represented.
In formula (3), X 1and X 2represent carbon atom or nitrogen-atoms independently of one another.Y 1represent oxygen atom or dicyano methylene.R 21to R 28represent hydrogen atom, halogen atom, nitro, substituted or unsubstituted alkyl or substituted or unsubstituted phenyl independently of one another.The substituting group of alkyl replaced and the substituent example of the phenyl of replacement comprise alkyl, haloalkyl, halogen atom, hydroxyl, carboxyl, mercapto, amino, methoxyl, nitro and cyano group.In addition, X is worked as 1and X 2during respective expression nitrogen-atoms, R 24and R 25all do not exist.
Benzimidazole compound is such as, has the compound of benzimidazole ring structure.In addition, the compound with the structure that wherein aromatic ring condenses mutually allows.The compound that benzimidazole compound is preferably represented by following formula (4), (5) or (6).
In formula (4), R 31to R 34represent hydrogen atom, halogen atom or alkyl independently of one another.M represents the repeat number of bracket inner structure, and represents 1 or 2.
In formula (5), R 41to R 44represent hydrogen atom, halogen atom or alkyl independently of one another.O represents the repeat number of bracket inner structure, and represents 1 or 2.
In formula (6), R 51and R 52represent hydrogen atom, halogen atom, nitro or substituted or unsubstituted alkyl independently of one another.R 53represent substituted or unsubstituted alkyl, substituted or unsubstituted phenyl or substituted or unsubstituted naphthyl.The substituent example of the substituting group of alkyl replaced, the substituting group of the phenyl of replacement and the naphthyl of replacement comprises alkyl, hydroxyalkyl, haloalkyl, halogen atom, hydroxyl, carboxyl, mercapto, amino, methoxyl, nitro and cyano group.P represents the repeat number of bracket inner structure, and represents 1 or 2.
Cyclopentadienyl compounds is such as, has the compound of cyclopentadienyl structure.In addition, the compound that wherein aromatic ring condenses mutually allows.The compound that cyclopentadienyl compounds is preferably represented by following formula (7).
In formula (7), X 3and X 4represent carbon atom or nitrogen-atoms independently of one another.Y 2represent oxygen atom, dicyano methylene or substituted or unsubstituted phenylimino.The substituting group of the phenylimino replaced is such as, alkyl.R 61to R 68represent hydrogen atom, alkoxy carbonyl group or nitro independently of one another.In addition, X is worked as 3and X 4during respective expression nitrogen-atoms, R 64and R 65all do not exist.
Due to following reason, the electron transport material in the present invention preferably shows the compound of poor solubleness in water.In water, show the index of poor solubleness as electron transport material, the electron transport Material Definitions meeting following condition is indissoluble: when the sub-transportation of substances mixing of power and water, the ratio of the electron transport material be dissolved in the water is below 0.5 quality %.
When using crosslinking chemical or having the resin of polymerizable functional group, electron transport material preferably has the electron transport material of polymerizable functional group.The example of polymerizable functional group comprises hydroxyl, mercapto, amino, carboxyl and methoxyl.
Next, crosslinking chemical is described.Crosslinking chemical of the present invention be have can with there is the resin of polymerizable functional group or there is the compound of group of electron transport substance reaction of polymerizable functional group.Particularly, such as, the compound recorded in " the Crosslinking Agent Handbook " that edited by Shinzo Yamashita and Tosuke Kaneko published by TAISEISHA LTD. (1981) can be used.Such as, preferred isocyanate compound or amines.
Isocyanate compound preferably has the isocyanate compound of the isocyanate group of 3-6 isocyanate group or end-blocking.
The isocyanate group of end-blocking is for having by-NHCOX 1(wherein X 1represent blocking group) group of structure that represents.Although X 1any blocking group can be represented, as long as described group can introduce isocyanate group, but X 1more preferably represent by any one group represented of following formula (H1) to (H7).
The instantiation of isocyanate compound is shown below.
In addition, amines is preferably any one compound represented by following formula (C1) to (C5), or by any one oligomer of compound represented of following formula (C1) to (C5).
Formula (C1) in (C5), R 11to R 16, R 22to R 25, R 31to R 34, R 41to R 44and R 51to R 54represent hydrogen atom, hydroxyl, acyl group or by-CH independently of one another 2-OR 1the monoradical represented, and R 11to R 16one of at least, R 22to R 25one of at least, R 31to R 34one of at least, R 41to R 44one of at least and R 51to R 54represent by-CH one of at least separately 2-OR 1the monoradical represented.R 1represent hydrogen atom or there is more than 1 and the alkyl of less than 10 carbon atoms.From the viewpoint of polymerism, described alkyl is preferably such as, methyl, ethyl, propyl group (n-pro-pyl or isopropyl) or butyl (normal-butyl, isobutyl or the tert-butyl group).R 21represent the naphthenic base that aryl, naphthenic base or alkyl that aryl, alkyl replace replace.
Illustrate below by the instantiation of any one compound represented of formula (C1) to (C5).In addition, can be mixed into by the oligomer of any one compound represented of formula (C1) to (C5).Two or more oligomer and the monomer of potpourri can be used as.
Illustrate below by the instantiation of any one compound represented of formula (C1) to (C5).In formula, Bu represents butyl.
Next, resin is described.Described resin can be mixed in the solution comprising electron transport material.The example of described resin comprises vibrin, polycarbonate resin, polyvinyl butyral, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenolics and alkyd resin.In addition, when use has electron transport material and the crosslinking chemical of polymerizable functional group, the resin with polymerizable functional group is preferably used.The example with the resin of polymerizable functional group comprises the resin separately with the structural unit represented by following formula (D).
In formula (D), R 61represent halogen atom or alkyl, Y 1represent singly-bound, alkylidene or phenylene, and W 1represent hydroxyl, mercapto, amino, carboxyl or methoxyl.W 1represent polymerizable functional group.
The example with the thermoplastic resin of the structural unit represented by formula (D) comprises acetal resin, polyolefin resin, vibrin, polyether resin and polyamide.Described resin can have the structural unit represented by formula (D) in any one of the following feature structure illustrated, or can have the structural unit except feature structure.Feature structure is represented by following formula (E-1) to (E-5).Formula (E-1) represents the structural unit of acetal resin.Formula (E-2) represents the structural unit of polyolefin resin.Formula (E-3) represents the structural unit of vibrin.Formula (E-4) represents the structural unit of polyether resin.Formula (E-5) represents the structural unit of polyamide.
In formula, R 201to R 205represent substituted or unsubstituted alkyl or substituted or unsubstituted aryl independently of one another.Work as R 201represent C 3h 7time, feature structure is called " butyral ".In formula, R 206to R 210represent substituted or unsubstituted alkylidene or substituted or unsubstituted arlydene independently of one another.
The resin (being hereinafter sometimes referred to as " resin D ") with the structural unit represented by formula (D) is by will such as, purchased from Sigma-Aldrich Japan K.K. or Tokyo Chemical Industry, the monomer polymerization with polymerizable functional group of Co., Ltd. and obtaining.
Determine that the example of the method for the polymerizable functional group in resin comprises following method: the titration using the carboxyl of potassium hydroxide; Use the titration of the amino of sodium nitrite; Use the titration of the hydroxyl of acetic anhydride and potassium hydroxide; Use the titration of the mercapto of 5,5'-bis-thiobis (2-nitrobenzoic acid); With relate to the method for calibration curve used by wherein changing IR spectrum that polymerizable functional group introduces the sample of ratio and obtaining.
Table 1 illustrates the instantiation of resin D." feature structure " row in table 1 illustrate any one structural unit represented by formula (E-1) to (E-5).In the present invention, the weight-average molecular weight of resin refer to that the method by recording in common method particularly Japanese Patent Application Laid-Open No.2007-79555 measures with the weight-average molecular weight of polystyrene basis.
(table 1)
The content of electron transport material is preferably more than 30 quality % and below 70 quality %, relative to the gross mass of entire solid matters in emulsion.
In addition, roughening particle (roughening particle) can be mixed in electron supplying layer as adjuvant.The example of roughening particle comprises particle and the metal oxide particle of curable resin.In addition, adjuvant can be mixed into as silicone oil, surfactant or silane compound.
In the present invention, be used in the liquid (hydrophobic solvent) that solubleness in the water under 25 DEG C and 1 atmospheric pressure is below 3.0 quality %.Table 2 illustrates the representative instance of hydrophobic solvent.In addition, the term " in water solubleness " in table to represent under 25 DEG C and 1 atmospheric pressure (atmospheric pressure) solubleness in the water of quality % unit.
(table 2)
No. Title Solubleness in water
1 Toluene 0.1 quality %
2 Chloroform 0.8 quality %
3 O-dichlorobenzene 0.0 quality %
4 Chlorobenzene 0.1 quality %
5 O-xylene 0.0 quality %
6 Ethylbenzene 0.0 quality %
7 Cyclohexanone 2.8 quality %
8 2-HEPTANONE 0.4 quality %
Wherein, from the viewpoint of the stabilization of emulsion, preferred toluene, dimethylbenzene or cyclohexanone.The two or more hydrophobic solvent of potpourri can be used as.
Preferably except hydrophobic solvent, the liquid (hydrophilic solvent) being also more than 5.0 quality % by solubleness in the water under 25 DEG C and 1 atmospheric pressure is mixed in solution of the present invention.Its instantiation comprises tetrahydrofuran, dimethoxymethane, 2-butanone, 1, 2-diox, 1, 3-diox, 1, 4-diox, 1, 3, 5-trioxane, methyl alcohol, 2 pentanone, ethanol, oxinane, diethylene glycol dimethyl ether, glycol dimethyl ether, propylene glycol n-butyl ether, propylene glycol monopropyl ether, glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol list isobutyl ether, ethylene glycol monoallyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Tripropylene glycol monomethyl Ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, diglycol ethyl methyl ether, diethyl carbitol, dimethyl ether, propylene-glycol diacetate, methyl acetate, ethyl acetate, n-propanol, 3-methoxybutanol, 3-methoxybutyl acetic acid esters and ethylene glycol monomethyl ether acetate.Table 3 illustrates these hydrophilic solvents solubleness separately.In addition, in table, term " in water solubleness " to refer under 25 DEG C and 1 atmospheric pressure (atmospheric pressure) solubleness in the water of quality % unit.
(table 3)
No. Title Solubleness in water
1 Tetrahydrofuran 100.0 more than quality %
2 Dimethoxymethane 32.3 quality %
3 2-butanone 22.3 quality %
4 1,2-diox 100.0 more than quality %
5 1,3-diox 100.0 more than quality %
6 1.4-diox 100.0 more than quality %
7 1,3,5-trioxane 21.1 quality %
8 Methyl alcohol 100.0 more than quality %
9 2 pentanone 5.9 quality %
10 Ethanol 100.0 more than quality %
11 Oxinane 100.0 more than quality %
12 Diethylene glycol dimethyl ether 100.0 more than quality %
13 Glycol dimethyl ether 100.0 more than quality %
14 Propylene glycol n-butyl ether 6.0 quality %
15 Propylene glycol monopropyl ether 100.0 more than quality %
16 Ethylene glycol monoethyl ether 100.0 more than quality %
17 Diethylene glycol monoethyl ether 100.0 more than quality %
18 Ethyleneglycol monopropylether 100.0 more than quality %
19 Ethylene glycol monobutyl ether 100.0 more than quality %
20 Ethylene glycol list isobutyl ether 100.0 more than quality %
21 Ethylene glycol monoallyl ether 100.0 more than quality %
22 Propylene glycol monomethyl ether 100.0 more than quality %
23 Dipropylene glycol monomethyl ether 100.0 more than quality %
24 Tripropylene glycol monomethyl Ether 100.0 more than quality %
25 Propylene glycol monobutyl ether 6.4 quality %
26 Propylene glycol monoethyl ether acetate 20.5 quality %
27 Diglycol ethyl methyl ether 100.0 more than quality %
28 Diethyl carbitol 100.0 more than quality %
29 Dimethyl ether 37.0 quality %
30 Propylene-glycol diacetate 7.4 quality %
31 Methyl acetate 19.6 quality %
32 Ethyl acetate 8.3 quality %
33 N-propanol 100.0 more than quality %
34 3-methyl cellosolve 100.0 more than quality %
35 3-methoxybutyl acetic acid esters 6.5 quality %
36 Ethylene glycol monomethyl ether acetate 100.0 more than quality %
Wherein, preferred ether solvent, and in ether solvent, from the viewpoint of emulsion stabilization, more preferably tetrahydrofuran, 2-butanone or dimethoxymethane.The two or more hydrophilic solvent of potpourri can be used as.Especially, when being formed on supporting mass by dip-coating when the film of emulsion when film being coated on the step on following supporting mass, preferably use the hydrophilic solvent with relatively low boiling point such as less than 100 DEG C.This is due to following reason: rapid solvent removal in the step of heating film, thus easily can control the homogeneity on the surface of undercoat.
In water under 25 DEG C and 1 atmospheric pressure, solubleness is that the quality of the liquid of below 3.0 quality % is represented by (a), and in the water under 25 DEG C and 1 atmospheric pressure, solubleness is that the quality of the liquid of more than 5.0 quality % is represented by (b).Now, the ratio (a/b) of (a) and (b) is preferably 1/9 to 9/1, and more preferably 2/8 to 9/1.Thus, in the step of following production emulsion, in emulsion, the diameter of oil droplet reduces, therefore emulsion stabilization extraordinarily.
When preparing emulsion, from the viewpoint of stability of emulsion, the viscosity comprising the solution of electron transport material is preferably set to and falls in appropriate scope.Particularly, electron transport material and any other undercoat constituent material preferably dissolve with the ratio in the scope of more than 3 quality % to below 50 quality %, relative to the gross mass of hydrophobic solvent and hydrophilic solvent.The viscosity of solution preferably drops in the scope of more than 1mPas to below 300mPas.
Next, be described through the step of Solution Dispersion galactopoiesis in next life liquid in water.
Existing method can be used as the method preparing emulsion.Hereinafter, describe paddling process and high-pressure impingement method as concrete grammar, but production method of the present invention is not limited thereto.
Stirring means is described.By undercoat constituent material as resin and crosslinking chemical and electron transport substance dissolves in hydrophobic solvent to prepare solution.After taking described solution, take the water as dispersion medium, and mix described solution and water.Afterwards, potpourri stirring machine is stirred.Here, from the viewpoint of electrofax characteristic, the water that be used as dispersion medium is preferably therefrom the ion exchange water of the removing such as spent ion exchange resin metallic ion etc.The conductance of ion exchange water is preferably 5 below μ S/cm.Stirring machine preferably can the stirring machine of high-speed stirred, because can disperse uniformly at short notice, and described machine is such as, homogenizer.
High-pressure impingement method is described.By undercoat constituent material as resin and crosslinking chemical and electron transport substance dissolves in hydrophobic solvent to prepare solution.After taking described solution, take the water as dispersion medium, and mix described solution and water.Afterwards, mixing material is under high pressure collided mutually, can emulsion be obtained thus.In addition, emulsion can by making when not having mixing material to collide mutually as the described solution of independent liquid and aqueous phase to obtain.Dispersing apparatus is such as, microfluidizer (microfluidizer).
In emulsion, the quality of water is represented by (w), the quality of hydrophobic solvent is represented by (a), the quality of hydrophilic solvent is represented by (b), the quality of electron transport material is represented by (ct), the quality of resin is represented by (r), and the quality of crosslinking chemical is represented by (k).Now, from the viewpoint of emulsion stabilization, (w) is preferably 4/6 to 8/2 with the ratio (w/ (a+b+r+ct+k)) of (a+b+r+ct+k).Described ratio is more preferably 5/5 to 7/3.In addition, make the viewpoint of emulsion stabilization from the diameter reducing each oil droplet emulsion, the ratio of water and organic solvent (hydrophobic solvent and hydrophilic solvent) is preferred high as much as possible.
In each oil droplet, the ratio of undercoat constituent material as resin and crosslinking chemical and electron transport material and organic solvent (hydrophobic solvent and hydrophilic solvent) is preferably 3-50 quality %.Ratio between electron transport material and resin and/or crosslinking chemical drops on preferred 2:7 to 10:0 (mass ratio), in the scope of more preferably 3:7 to 7:3 (mass ratio).In addition, when adjuvant is added in material further, its ratio is preferably below 50 quality %, more preferably below 30 quality %, relative to the solid matter of electron transport material, resin and crosslinking chemical.
In addition, in order to the object surfactant of stabilization emulsification extraordinarily can be mixed in emulsion of the present invention.Surfactant is preferably non-ionic surfactant.The instantiation of non-ionic surfactant comprises: the NAROACTY manufactured by Sanyo Chemical Industries, Ltd. is serial, EMULMIN is serial, SANNONIC is serial and NEWPOL is serial; The EMULGEN manufactured by Kao Corporation is serial, RHEODOL is serial and EMANON is serial; The ADEKA TOL series manufactured by ADEKA CORPORATION, ADEKA ESTOL series and ADEKA NOL series; With a series of non-ionic surfactant in the NEWCOL series manufactured by NIPPON NYUKAZAI CO., LTD..Can be used alone the one of those surfactants, or can combinationally use that they are two or more.Never should damage the viewpoint of electrofax characteristic, the addition of surfactant is preferably little as much as possible.In emulsion, the content of surfactant drops on preferably 0 quality % to 5.0 quality %, in the scope of more preferably 0 quality % to 1.5 quality %.In addition, surfactant can be added in the water as dispersion medium in advance, or can be added into wherein dissolved electron transport material solution in.Alternatively, surfactant can be added into one of both medium and solution before emulsification.In addition, defoamer or viscoelasticity modifying agent etc. can be mixed in emulsion in the degree not damaging effect of the present invention, and when reagent is water-soluble, this type of reagent any is effective.
From the viewpoint of emulsion intercalation method, the mean grain size of each oil droplet of the emulsion of producing as mentioned above preferably drops in the scope of 0.1-20.0 μm.Mean grain size more preferably drops in the scope of 0.1-5.0 μm.
Next, the step of film supporting mass being formed emulsion is described in.
As the method for the film of formation masking liquid, provide such as, dip coating, ring are coated with method, spraying process, spin-coating method, rolling method, Meyer stick coating method and knife coating.Wherein, from productive viewpoint, preferred dip coating.
Next, the step of heating film is described.
The film that heating is formed on supporting mass is to form undercoat.Removing dispersion medium, meanwhile, is made the mutual close contact of oil droplet of each self-contained electron transport material, can form the undercoat with high uniformity thus by heating steps.The particle diameter of preferred each oil droplet reduces extraordinarily, because improve the homogeneity of primer thickness fast after removal of the dispersion medium.Carry out at the temperature of heating preferably more than 100 DEG C.In view of the cohesive between oil droplet is improved, heating-up temperature is more preferably equal to or greater than the fusing point of the electron transport material of the minimum fusing point had in the electron transport material forming undercoat, this is because can form the undercoat with especially high homogeneity.In addition, heating-up temperature is preferably less than 200 DEG C, because there is the distortion etc. of electron transport material when heating-up temperature is too high.
The thickness of undercoat is preferably more than 0.1 μm and less than 30 μm, more preferably more than 0.3 μm and less than 5 μm.
(supporting mass)
Supporting mass preferably has the supporting mass (conductive support) of electric conductivity.Such as, the supporting mass be made up as aluminium, nickel, copper, gold or iron or its alloy of metal can be used.The example comprises: by by metal as aluminium, silver or golden film-shaped are formed in by such as, the supporting mass that the insulating supporting body that vibrin, polycarbonate resin, polyimide resin or glass are made obtains; With by forming the supporting mass that conductive material obtains as the film of indium oxide or tin oxide.
Electrochemical treatment can be carried out as anodization in the surface of supporting mass, or the process such as such as wet type honing process, blasting treatment or machining, to improve electrology characteristic and to suppress interference condition.
Conductive layer can be formed between supporting mass and undercoat.Conductive layer is by following acquisition: on supporting mass, form the film by conductive particle being dispersed in the conductive layer coating fluid obtained in resin; And dry coating.The example of conductive particle comprises carbon black, acetylene black, by such as, and the metal powder that aluminium, nickel, iron, nichrome, copper, zinc and silver are made, and by such as, the metal oxide powder that conductive tin oxide and ITO make.
Example for the resin of conductive layer comprises vibrin, polycarbonate resin, polyvinyl butyral resin, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenolics and alkyd resin.
Example for the solvent of conductive layer coating fluid comprises ether solvent, alcohols solvent, ketones solvent and aromatic hydrocarbons solvent.
The thickness of conductive layer is preferably more than 0.2 μm and less than 40 μm, more preferably more than 1 μm and less than 35 μm, still more preferably more than 5 μm and less than 30 μm.In addition, conductive layer can be formed between undercoat of the present invention and charge generation layer.
(charge generation layer)
Charge generation layer is formed on undercoat.
The example of charge generation substance comprises AZO pigments, perylene dye, indigo-blue derivant and phthalocyanine color.Wherein, preferred AZO pigments or phthalocyanine color one of at least.In phthalocyanine color, preferred titanyl phthalocyanine, gallium chlorine phthalocyaninate or hydroxy gallium phthalocyanine.
As the resin glue for charge generation layer, provide such as: as polymkeric substance and the multipolymer of the vinyl compounds such as styrene, vinyl acetate, vinyl chloride, esters of acrylic acid, methyl acrylic ester, vinylidene fluoride or trifluoro-ethylene; With polyvinyl alcohol resin, polyvinyl acetal resin, polycarbonate resin, vibrin, polysulfone resin, polyphenylene oxide resin, urethane resin, celluosic resin, phenolics, melamine resin, silicones and epoxy resin.Wherein, preferred polyester resin, polycarbonate resin or polyvinyl acetal resin, more preferably polyvinyl acetal resin.
Charge generation layer can be formed by following: form the film by charge generation substance and resin being disperseed together with solvent the charge generation layer coating fluid obtained; With dry gained film.In addition, charge generation layer can be the deposited film of charge generation substance.
In charge generation layer, the mass ratio (charge generation substance/resin glue) of charge generation substance and resin glue drops on preferably 10/1 to 1/10, more preferably 5/1 to 1/5 scope in.
Example for the solvent of charge generation layer coating fluid comprises alcohols solvent, sulfoxide type solvents, ketones solvent, ether solvent, esters solvent and aromatic hydrocarbon solvent.The thickness of charge generation layer is preferably more than 0.05 μm and less than 5 μm.
In addition, arbitrary various emulsion, antioxidant, UV absorbing agent and plastifier etc. can be added in charge generation layer if needed.Electron transport material or electronics accept material and also can be mixed in charge generation layer to prevent the flow disruption of electric charge in charge generation layer.
(hole transporting layer)
Hole transporting layer is formed on charge generation layer.Hole transporting layer comprises cavity conveying material and resin glue.
The example of cavity conveying material comprises polynuclear aromatic compound, heterogeneous ring compound, hydrazone compound, compound of styryl, benzidine compound, triarylamine compounds, triphenylamine and in main chain or side chain, has the polymkeric substance of group of any one being derived from these compounds.Wherein, preferred triarylamine compounds, benzidine compound or compound of styryl.
As the resin glue for hole transporting layer, provide such as, vibrin, polycarbonate resin, polymethacrylate resin, polyarylate resin, polysulfone resin and polystyrene resin.Wherein, optimization polycarbonate resin and polyarylate resin.In addition, resin glue preferably has 10,000-300, and the weight-average molecular weight (Mw) of 000 is as its molecular weight.
In hole transporting layer, the mass ratio (cavity conveying material/resin glue) of hole transportation of substances and resin glue is preferably 10/5 to 5/10, more preferably 10/8 to 6/10.The thickness of hole transporting layer is preferably more than 3 μm and less than 40 μm, more preferably more than 5 μm and less than 16 μm.
In addition, hole transporting layer can also comprise adjuvant except cavity conveying material and resin glue.The instantiation of adjuvant comprises: deterioration preventing agent is as antioxidant, UV absorbing agent or light stabilizer; With the resin for giving release property.The example of deterioration preventing agent comprises hindered phenol anti-oxidants, hindered amine light stabilizer, sulfur atom-containing antioxidant and contains phosphorus atoms antioxidant.Example for the resin giving release property comprises contain fluorine atoms resin and has the resin of siloxane structure.
As the solvent for hole transporting layer coating fluid, provide such as, alcohols solvent, sulfoxide type solvents, ketones solvent, ether solvent, esters solvent or aromatic hydrocarbons solvent.
In addition, protective seam can be formed on hole transporting layer.Protective seam comprises conductive particle or charge transport material and resin glue.In addition, protective seam can comprise adjuvant further as lubricant.In addition, the resin glue of protective seam itself can give electric conductivity or charge-transporting.In this case, conductive particle in addition to the resins or charge transport material can not be mixed in protective seam.In addition, the resin glue of protective seam can be thermoplastic resin, or can be by utilizing such as, the polymerization of light, heat or radiation (as electron beam) and the curable resin that obtains.
Formation method as each layer preferably relates to following method: be coated with coating fluid by the material dissolves of constituting layer and/or be scattered in being obtained in solvent to form film; And drying and/or solidification gained film are to form layer.The example of the coating process of coating fluid comprises dip coating, spraying process, curtain coating processes and spin-coating method.Wherein, from efficiency and productive viewpoint, preferred dip coating.
(handle box and electronic photographing device)
Fig. 1 illustrates the schematic configuration comprising the electronic photographing device of the handle box comprising electrophotographic photosensitive element.
In Fig. 1, cylindric electrophotographic photosensitive element 1 can be driven to rotate under predetermined peripheral speed along the direction shown in arrow around axle 2.Charged under predetermined plus or minus current potential equably by charhing unit 3 (charhing unit: as charging roller) in the surface (side face) of the electrophotographic photosensitive element 1 be driven in rotation.Subsequently, the surface of electrophotographic photosensitive element 1 receives the exposure light (image exposure light) 4 exposed as slit exposure or laser beam flying from exposing unit (not shown).By this way, the electrostatic latent image corresponding to target image is formed on the surface of electrophotographic photosensitive element 1 successively.
Then the electrostatic latent image be formed on the surface of electrophotographic photosensitive element 1 changes toner image into by the toner development comprised in the developer with developing cell 5.Subsequently, to be formed and the toner image remained on the surface of electrophotographic photosensitive element 1 is transferred to transfer materials (as paper) P by transfer bias subsequently from transfer printing unit (as transfer roll) 6.It should be noted that transfer materials P takes out from the transfer materials feed unit (not shown) synchronous with the rotation of electrophotographic photosensitive element 1, and be fed to the part (contact site) between electrophotographic photosensitive element 1 and transfer printing unit 6.
The transfer materials P having received the toner image of transfer printing is separated from the surface of electrophotographic photosensitive element 1, then introduces fixation unit 8.Transfer materials P carries out the image fixing of toner image, then prints to outside equipment as image formed matter (printer or duplicating machine).
After the transfer printing of toner image, the surface of electrophotographic photosensitive element 1 is by cleaning by remaining developer (toner) after cleaning unit (as cleaning balde) 7 removing transfer printing.Subsequently, the surface of electrophotographic photosensitive element 1 uses the pre-exposure light (not shown) from pre-exposure unit (not shown) to carry out neutralisation treatment, is then repeatedly formed for image.It should be noted that as shown in fig. 1, when charhing unit 3 is the contact charhing unit using charging roller etc., always do not need pre-exposure.
Comprise in the construction package of electrophotographic photosensitive element 1, charhing unit 3, developing cell 5, transfer printing unit 6 and cleaning unit 7, multiple in them can be selected and lay in a reservoir, and integrated combination is handle box.The main body of electronic photographing device as duplicating machine or laser beam printer can be removably mounted to by design treatment box to make it.In Fig. 1, electrophotographic photosensitive element 1, charhing unit 3, developing cell 5 and cleaning unit 7 are integrated and support and be placed in box, formation processing box 9 thus.The track handle box 9 of pilot unit 10 as the main body of electronic photographing device is used removably to be mounted to the main body of electronic photographing device.
(embodiment)
Hereinafter, the present invention will by emulsion produce example and embodiment describe.But, the present invention is not limited thereto.It should be noted that " part " in embodiment refers to " mass parts ".
(emulsion production example 1)
The undercoat emulsion comprising electron transport material is produced by following method.
7 parts of compounds represented by following formula (A-1) (fusing point: 160-162 DEG C) as the resin (D1) recorded in electron transport material and 3 parts of tables 1 (in formula (E-1), R 201represent C 3h 7) be dissolved in 30 parts of toluene to prepare solution.Next, 1.5 parts of NOIGEN EA-167 are (by Dai-ichi Kogyo Seiyaku Co., Ltd. manufacture, HLB=14.8) be added in 58.5 parts of ion exchange waters (conductance: 0.2 μ S/cm) as surfactant, and at potpourri in 3, with while homogenizer, 40 parts of described solution are added into potpourri gradually through 10 minutes under 000 turn, prepare emulsion (100 parts) thus.In addition, be increased to 7 at revolution, while 000 turn, stir emulsion 20 minutes.Thus, emulsion 1 (100 parts) is obtained.
The liquid stability of evaluation gained emulsion as described below.
As evaluation method, emulsion leaves standstill 2 weeks (under the environment of the humidity of the temperature and 50% with 23 DEG C) after it is by described method preparation.Observe its state after the standing, then emulsion homogenizer is 1, stirs 3 minutes under 000 turn/min.Emulsion state after stirring uses eye observation equally.In addition, the particle diameter of emulsion particle (oil droplet) is measured in the measurement by carrying out their mean grain size after the stirring before leaving standstill and after leaving standstill.It should be noted that the measurement of mean grain size is carried out as follows: emulsion dilute with water, and the mean grain size of each emulsion particle uses the automatic particle size distribution measurement equipment (CAPA700) of the ultracentrifugation formula manufactured by HORIBA, Ltd. to measure.
The state of the emulsion obtained in production example 1 after leaving standstill is the state that wherein its mean grain size increases compared with mean grain size at once after its preparation.But emulsion is not separated and maintains its emulsified state.Table 5-1 is shown in evaluation result.
(emulsion produces routine 2-53)
Except in kind and the ratio of being prepared change electron transport material as shown in table 4, resin and crosslinking chemical in the emulsion comprising electron transport material by the method identical with emulsion production example 1; With change hydrophobic solvent and the ratio (mass ratio) of hydrophilic solvent and the kind of solvent, and beyond the ratio changing water and solvent as shown as shown in 5-1,5-2,6-1 and 6-2, prepare emulsion separately by the method identical with emulsion production example 1.Table 5-1,5-2,6-1 and 6-2 illustrate the evaluation result of the liquid stability of gained emulsion.When the isocyanate compound with blocked isocyanate base is used as crosslinking chemical, table 4 listed in by isocyanate compound and blocked isocyanate base.
It should be noted that and to be expressed from the next for the electron transport material in emulsion production example.The fusing point of the compound represented by following formula (A-2) is 180-181 DEG C and the fusing point of compound that represented by following formula (A-3) is 120-122 DEG C.The concrete structure of the feature structure (E-1) of D25 is as follows: D25 has two kinds of structures, i.e. wherein R 201represent CH 3structure and wherein R 201represent C 2h 5structure.In the feature structure (E-3) of D20, R 206represent CH 2and R 207represent CH 2.
In addition, the kind of producing the surfactant of example for emulsion is as described below.Produce in routine 1-28,40-45 and 51-53 in each emulsion, use NOIGEN EA-167 (being manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., HLB=14.8).Produce in routine 29-33 in each emulsion, use NAROACTY CL-85 (being manufactured by Sanyo Chemical Industries, Ltd., HLB=12.6).Produce in routine 34-39 in each emulsion, use EMULGEN MS-110 (being manufactured by Kao Corporation, HLB=12.7).
In addition, routine catalyzer is produced for emulsion as described below.Produce in routine 7-39 and 48-53 in each emulsion, use 0.03 part of dioctyl tin cinnamic acid tin.Produce in routine 40-45 in each emulsion, use 0.1 part of dodecylbenzene sulfonic acid.
(table 4)
(table 5-1)
(table 5-2)
(table 6-1)
(table 6-2)
Produce example according to emulsion, the emulsion comprising electron transport material can be prepared.Especially, even if the emulsion also stably maintaining its emulsified state and demonstrate little change in long storage periods state compared with its virgin state obtains by relating to following method: prepare solution by using the solvent comprising both hydrophobic solvent and hydrophilic solvent; By described Solution Dispersion in water to prepare emulsion.
According to described method, the content of the organic solvent (halogen based solvents or arsol) the electron transport material in emulsion to high-dissolvability can be reduced, and emulsion has good long-term liquid stability, and thus emulsion can be used as coating liquid for undercoat layer.
(embodiment 1)
The aluminium cylinder with 30mm diameter and 260.5mm length is used as supporting mass (conductive support).
Next, 10 parts of SnO 2the mixed solvent of the barium sulphate (conductive particle) of coating process, 2 parts of titanium dioxide (resistance adjustment pigment), 6 parts of phenolics, 0.001 part of silicone oil (levelling agent) and 4 parts of methyl alcohol and 16 parts of methoxypropanol is for the preparation of conductive layer coating fluid.Conductive layer coating fluid is coated on to form film on supporting mass by dip-coating, and gained film heats (heat curing) 30 minutes thus forms the conductive layer with 15 μm of thickness at 140 DEG C.
Next, the emulsion of producing in emulsion production example 1 is coated with on the electrically conductive to form film by dip-coating.Carry out at 165 DEG C, heat the gained film step of 1 hour thus form the undercoat with 2.0 μm of thickness.Table 7 illustrates the condition of the emulsion (emulsion produces example) of use and the film of heating emulsion.It should be noted that emulsion is the emulsion through following process: emulsion leave standstill 2 weeks (the temperature of 23 DEG C and 50% humidity under), then use homogenizer 1, under 000 turn/min stir 3 minutes.Film is formed by dip-coating by means of use emulsion.
Next, prepare 10 parts of hydroxygallium phthalocyanine crystals (in the X-ray diffraction of CuK α feature be that 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° places have strong peak at Bragg angle (2 θ ± 0.2 °)), then with 250 parts of cyclohexanone and 5 parts of acetal resin (trade names: S-LEC BX-1, manufactured by SEKISUI CHEMICAL CO., LTD.) mixing.Gained potpourri disperses 1 hour under 23 ± 3 DEG C of atmosphere by using the sand mill equipment separately with the beaded glass of 1mm diameter.After dispersion, add 250 parts of ethyl acetate to prepare charge generation layer coating fluid.Charge generation layer coating fluid is coated on to form film on undercoat by dip-coating, and gained film at 100 DEG C dry 10 minutes thus form the charge generation layer with 0.26 μm of thickness.
Next, (ratio with 5/5 has the structural unit represented by following formula (9-1) and the structural unit represented by following formula (9-2) for 8 parts of amines represented by following formula (8) (cavity conveying material) and 10 parts of vibrin, and having weight-average molecular weight (Mw) is 100,000) be dissolved in the mixed solvent of 40 parts of dimethoxymethane and 60 parts of o-xylenes to prepare hole transporting layer coating fluid.Hole transporting layer coating fluid is coated on to form film on charge generation layer by dip-coating, and gained film at 120 DEG C dry 40 minutes thus form the hole transporting layer with 15 μm of thickness.Thus, electrophotographic photosensitive element is obtained.
Next, evaluation is described.
The evaluation > of the homogeneity of < base coating surface
Except above-mentioned electrophotographic photosensitive element, also the emulsion of producing in emulsion production example 1 is coated on by dip-coating on the aluminium cylinder with 30mm diameter and 260.5mm length to form film.Gained film at 165 DEG C dry 1 hour thus form the undercoat with 2.0 μm of thickness.
About its surfaceness, measure the surface of gained undercoat in the position of the fore-and-aft distance upper end 130mm along aluminium cylinder with measuring device for surface roughness (Surfcorder SE-3400 is manufactured by Kosaka Laboratory Ltd.).Being measured as of surfaceness evaluates based on 10 mean roughness (Rzjis) evaluation (evaluation length: 10mm) carried out in JIS B0601:2001.Table 7 illustrates result.
< picture appraisal >
Picture appraisal is carried out by the laser beam printer LBP-2510 being used for being manufactured by Canon Inc. by the electrophotographic photosensitive element of production.In picture appraisal, about the charging potential (dark space current potential) of electrophotographic photosensitive element and the exposure value (image exposure value) of 780-nm LASER Light Source, carry out transforming to make the light quantity on the surface of electrophotographic photosensitive element become 0.3 μ J/cm 2.In addition, evaluate under the environment of the relative humidity of the temperature and 50% with 23 DEG C.Carry out picture appraisal as follows: monochromatic half tone image exports in A4 size common paper, and by following standard visual valuation output image.Grade A and grade B is respectively customized for the level obtaining effect of the present invention.Table 7 illustrates result.
Grade A: see completely uniform image.
Grade B: see slight image heterogeneity.
Grade C: see image heterogeneity.
Grade D: see outstanding image heterogeneity.
(embodiment 2-50 and 54-56)
Except: undercoat is formed by using the emulsion recorded in table 7; Beyond the condition of the film of the change heating emulsion recorded in such as table 7, produce electrophotographic photosensitive element separately by the method identical with embodiment 1.Electrophotographic photosensitive element is by those the identical method evaluations with embodiment 1.Table 7 illustrates result.
(embodiment 51-53)
Except in the step forming undercoat, emulsion does not leave standstill 2 weeks after its preparation, in 1 hour, emulsion is coated with on the electrically conductive to form film and to heat beyond film by dip-coating after emulsion preparation, produces electrophotographic photosensitive element separately by the method identical with embodiment 1.Electrophotographic photosensitive element is by those the identical method evaluations with embodiment 1.Table 7 illustrates result.
(embodiment 57-59)
Except in the step forming undercoat, the thickness of film after its heating is set as, beyond 1.0 μm, producing electrophotographic photosensitive element separately by the method identical with embodiment 1.Electrophotographic photosensitive element is by those the identical method evaluations with embodiment 1.Table 7 illustrates result.
(comparative example 1)
Except its undercoat of formation as described below, by producing with those identical methods of embodiment 1 and evaluate electrophotographic photosensitive element.Table 8 illustrates result.
5 parts of compounds represented by formula (A-1) and 5 parts of resins (D1) are dissolved in 30 parts of tetrahydrofurans to prepare solution.Next, 3 parts of surfactants (NOIGEN EA-167) are added in 57 parts of ion exchange waters (conductance: 0.2 μ S/cm), and at potpourri in 3, with while homogenizer, 40 parts of described solution are added into potpourri gradually through 10 minutes under 000 turn, prepare coating liquid for undercoat layer (100 parts) thus.In addition, 7 are increased at revolution, agitated liquid 20 minutes while 000 turn.Thus, coating liquid for undercoat layer (coating fluid production example 1,100 parts) is obtained.
By the liquid stability of the method evaluation gained coating liquid for undercoat layer identical with emulsion production example 1.When after the preparation of coating fluid at once visualization coating fluid time, its color is opaque white color.The mean grain size of each oil droplet at top place is 35.6 μm.But, observe several peak, and the particle diameter of oil droplet is uneven.In addition, after coating fluid leaves standstill 2 weeks, coating fluid is separated, and thus can not carry out grain diameter measurement.
Except in the step forming undercoat, coating fluid does not leave standstill 2 weeks after its preparation, with coating fluid is coated with on the electrically conductive by dip-coating in 1 hour after the preparation of coating fluid thus is formed beyond film, form undercoat by method in the same manner as in Example 1.
(comparative example 2)
Except its undercoat of formation as described below, by producing with those identical methods of embodiment 1 and evaluate electrophotographic photosensitive element.Table 8 illustrates result.
Coating fluid production example 2 is prepared by the organic solvent of the coating fluid production example 1 recorded in comparative example 1 is become 30 parts of 2-butanone from 30 parts of tetrahydrofurans.
By the liquid stability of the method evaluation gained coating liquid for undercoat layer identical with emulsion production example 1.When after the preparation of coating fluid at once visualization coating fluid time, its color is opaque white color.The mean grain size of each oil droplet at top place is 32.1 μm.But, observe several peak, and the particle diameter of oil droplet is uneven.In addition, after coating fluid leaves standstill 2 weeks, coating fluid is separated, and thus can not carry out grain diameter measurement.
Except in the step forming undercoat, coating fluid does not leave standstill 2 weeks after its preparation, with coating fluid is coated with on the electrically conductive by dip-coating in 1 hour after the preparation of coating fluid thus is formed beyond film, form undercoat by method in the same manner as in Example 1.
(comparative example 3)
Except its undercoat of formation as described below, by producing with those identical methods of embodiment 1 and evaluate electrophotographic photosensitive element.Table 8 illustrates result.
By the organic solvent of coating fluid production example 1 recorded in comparative example 1 being become 15 parts of 2 pentanones from 30 parts of tetrahydrofurans and 15 parts of tetrahydrofurans prepare coating fluid production example 3.
By the liquid stability of the method evaluation gained coating liquid for undercoat layer identical with emulsion production example 1.When after the preparation of coating fluid at once visualization coating fluid time, its color is opaque white color.The mean grain size of each oil droplet at top place is 22.4 μm.But, observe several peak, and the particle diameter of oil droplet is uneven.In addition, after coating fluid leaves standstill 2 weeks, coating fluid is separated, and thus can not carry out the grain diameter measurement of oil droplet.
Except in the step forming undercoat, coating fluid does not leave standstill 2 weeks after its preparation, with coating fluid is coated with on the electrically conductive by dip-coating in 1 hour after the preparation of coating fluid thus is formed beyond film, form undercoat by method in the same manner as in Example 1.
(comparative example 4)
Except its undercoat of formation as described below, by producing with those identical methods of embodiment 1 and evaluate electrophotographic photosensitive element.Table 8 illustrates result.
By the organic solvent of the coating fluid production example 1 recorded in comparative example 1 being become 15 parts of oxalates (in its water under 25 DEG C and 1 atmospheric pressure, solubleness is 3.6 quality %) from 30 parts of tetrahydrofurans and 15 parts of tetrahydrofurans prepare coating fluid production example 4.
By the liquid stability of the method evaluation gained coating liquid for undercoat layer identical with emulsion production example 1.When after the preparation of coating fluid at once visualization coating fluid time, its color is opaque white color.The mean grain size of each oil droplet at top place is 20.5 μm.But, observe several peak, and the particle diameter of oil droplet is uneven.In addition, after coating fluid leaves standstill 2 weeks, coating fluid is separated, and thus can not carry out grain diameter measurement.
Except in the step forming undercoat, coating fluid does not leave standstill 2 weeks after its preparation, with coating fluid is coated with on the electrically conductive by dip-coating in 1 hour after the preparation of coating fluid thus is formed beyond film, form undercoat by method in the same manner as in Example 1.
(comparative example 5)
Except its undercoat of formation as described below, by producing with those identical methods of embodiment 1 and evaluate electrophotographic photosensitive element.Table 8 illustrates result.
The coating liquid for undercoat layer comprising electron transport material is prepared by following method.
5 parts of compounds represented by formula (A-3) are dissolved in 30 parts of tetrahydrofurans to prepare undercoat solution as crosslinking chemical and 0.03 part of dioctyl tin cinnamic acid tin as electron transport material, 2 parts of resins (D1), 3 parts of compounds represented by formula (B1:H1).Next, 3 parts of surfactants (NOIGEN EA-167) are added in 57 parts of ion exchange waters (conductance: 0.2 μ S/cm), and at potpourri in 3, with while homogenizer, 40 parts of described solution are added into potpourri gradually through 10 minutes under 000 turn, prepare coating liquid for undercoat layer (100 parts) thus.In addition, 7 are increased at revolution, agitated liquid 20 minutes while 000 turn.Thus, coating liquid for undercoat layer (coating fluid production example 5,100 parts) is obtained.
By the liquid stability of the method evaluation gained coating liquid for undercoat layer identical with emulsion production example 1.When after the preparation of coating fluid at once visualization coating fluid time, its color is opaque white color.The mean grain size of each oil droplet at top place is 38.4 μm.But, observe several peak, and the particle diameter of oil droplet is uneven.In addition, after coating fluid leaves standstill 2 weeks, coating fluid is separated, and thus can not carry out the grain diameter measurement of oil droplet.
Except in the step forming undercoat, coating fluid does not leave standstill 2 weeks after its preparation, with coating fluid is coated with on the electrically conductive by dip-coating in 1 hour after the preparation of coating fluid thus is formed beyond film, form undercoat by method in the same manner as in Example 1.
(comparative example 6)
Except its undercoat of formation as described below, by producing with those identical methods of embodiment 1 and evaluate electrophotographic photosensitive element.Table 8 illustrates result.
By the organic solvent of coating fluid production example 5 recorded in comparative example 5 being become 15 parts of oxalates from 30 parts of tetrahydrofurans and 15 parts of tetrahydrofurans prepare coating fluid production example 6.
By the liquid stability of the method evaluation gained coating liquid for undercoat layer identical with emulsion production example 1.When after the preparation of coating fluid at once visualization coating fluid time, its color is opaque white color.The mean grain size of each oil droplet at top place is 22.2 μm.But, observe several peak, and the particle diameter of oil droplet is uneven.In addition, after coating fluid leaves standstill 2 weeks, coating fluid is separated, and then can not carry out the grain diameter measurement of oil droplet.
Except in the step forming undercoat, coating fluid does not leave standstill 2 weeks after its preparation, with coating fluid is coated with on the electrically conductive by dip-coating in 1 hour after the preparation of coating fluid thus is formed beyond film, form undercoat by method in the same manner as in Example 1.
(table 7)
(table 8)
The comparison of embodiment and comparative example 1-6 demonstrates provides good image output by means of using emulsion of the present invention to form film and heating the electrophotographic photosensitive element that this film obtains to form undercoat.When solubleness in only water is used as solvent more than the liquid of 3.0 quality %, the particle diameter of oil droplet is large and just observe multiple particle diameter peak from time point at once after the preparation of coating fluid.Therefore, find that particle diameter is uneven.Even if when each coating fluid of comparative example 1-6 be formed as film when not leaving standstill and heating film thus form undercoat time, the homogeneity of undercoat is low and significantly observe image heterogeneity.This may be because the gathering of the oil droplet of coating fluid occurs due to the coalescent of oil droplet thus damages the homogeneity of oil droplet in emulsion, and thus the homogeneity of base coating surface reduces.
Although reference example embodiment describes the present invention, it should be understood that and the invention is not restricted to disclosed exemplary.The scope of following claim should with explain the most widely consistent, to contain these type of amendments all and equal 26S Proteasome Structure and Function.

Claims (11)

1. the production method of an electrophotographic photosensitive element, described electrophotographic photosensitive element comprises supporting mass, the undercoat be formed on described supporting mass, the hole transporting layer that is formed at the charge generation layer on described undercoat and is formed on described charge generation layer, and described method comprises:
Preparation comprises following solution:
In water under 25 DEG C and 1 atmospheric pressure, solubleness is the liquid of below 3.0 quality %, and
Electron transport material;
By described Solution Dispersion is prepared emulsion in water;
Described supporting mass is formed the film of described emulsion; With
Described undercoat is formed by heating described film.
2. the production method of electrophotographic photosensitive element according to claim 1, it is the liquid of more than 5.0 quality % that wherein said solution is included in solubleness in the water under 25 DEG C and 1 atmospheric pressure further.
3. the production method of electrophotographic photosensitive element according to claim 2, in wherein said water under 25 DEG C and 1 atmospheric pressure, solubleness is that the liquid of more than 5.0 quality % is for being selected from by tetrahydrofuran, dimethoxymethane, 2-butanone, 1,2-diox, 1,3-diox, Isosorbide-5-Nitrae-diox, 1,3,5-trioxane, methyl alcohol, 2 pentanone, ethanol, oxinane, diethylene glycol dimethyl ether, glycol dimethyl ether, propylene glycol n-butyl ether, propylene glycol monopropyl ether, glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol list isobutyl ether, ethylene glycol monoallyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Tripropylene glycol monomethyl Ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, diglycol ethyl methyl ether, diethyl carbitol, dimethyl ether, propylene-glycol diacetate, methyl acetate, ethyl acetate, n-propanol, 3-methoxybutanol, in the group of 3-methoxybutyl acetic acid esters and ethylene glycol monomethyl ether acetate composition one of at least.
4. the production method of electrophotographic photosensitive element according to claim 3, in wherein said water under 25 DEG C and 1 atmospheric pressure solubleness to be the liquid of more than 5.0 quality % be selected from the group be made up of tetrahydrofuran, 2-butanone and methyl alcohol one of at least.
5. the production method of electrophotographic photosensitive element according to claim 2, wherein said solution comprises resin further.
6. the production method of electrophotographic photosensitive element according to claim 5, wherein:
Described electron transport material is the electron transport material with polymerizable functional group; With
Described solution comprises the resin and crosslinking chemical with polymerizable functional group further.
7. the production method of electrophotographic photosensitive element according to claim 2, wherein:
Described electron transport material is the electron transport material with polymerizable functional group; With
Described solution comprises crosslinking chemical further.
8. the production method of electrophotographic photosensitive element according to claim 6, in wherein said emulsion, (w) is 5/5 to 7/3 with the ratio (w/ (a+b+r+ct+k)) of (a+b+r+ct+k), wherein " w " represents the quality of water in described emulsion, " a " represents that in the water described in described emulsion under 25 DEG C and 1 atmospheric pressure, solubleness is the quality of the liquid of below 3.0 quality %, " b " represents that in the water described in described emulsion under 25 DEG C and 1 atmospheric pressure, solubleness is the quality of the liquid of more than 5.0 quality %, " ct " represents the quality of electron transport material described in described emulsion, " r " represents the quality of resin described in described emulsion, " k " represents the quality of crosslinking chemical described in described emulsion.
9. the production method of electrophotographic photosensitive element according to claim 2, in wherein said emulsion, (a) is 1/9 to 9/1 with the ratio (a/b) of (b), during wherein " a " represents described in described emulsion under 25 DEG C and 1 atmospheric pressure water, solubleness is the quality of the liquid of below 3.0 quality %, and " b " represent described in described emulsion under 25 DEG C and 1 atmospheric pressure water in solubleness be the quality of the liquid of more than 5.0 quality %.
10. the production method of electrophotographic photosensitive element according to claim 1, wherein said electron transport material be selected from the group that is made up of imide compound, naphtoquinone compounds and benzimidazole compound one of at least.
The production method of 11. electrophotographic photosensitive elements according to claim 1, in wherein said water under 25 DEG C and 1 atmospheric pressure solubleness to be the liquid of below 3.0 quality % be selected from the group be made up of cyclohexanone, toluene and dimethylbenzene one of at least.
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